Process for the manufacture of condensation products from nonaliphatic sulphamides and aldehydes



Patented Mar. 9, 1937 UNITED STATES PROCESS FOR THE MANUFACNEE OFCONDENSATION PRODUCTS FROM NON- ALIPHATIC SULPHAMIDES mas AND ALDE-Georg Walter, Vienna, Austria No Drawing. Application July ll, 1932,Serial 28 Claims.

This invention relates to the manufacture of condensation products fromnon-aliphatic sulphamides and aldehydes. s

It is known to condense arylsulphamides and 5 theirN-monoalkyl-substiution products with formaldehyde. Soluble and fusibleartificial resins are obtained thereby, which products,-however, cannotbe hardened contrarily to the property'ot phenol-formaldehydecondensation prod- 10 nets and the urea-formaldehyde condensationproducts, that is to say they cannot be converted intothe insoluble andiniusible state by the action of heat.

The present invention is based on the discovery 1 that artificial resinscapable of being hardened can be obtained by condensing sulphamides ofcyclic organic compounds with aldehydes, provided that.

the sulphamides are such that contain at least one carbamyl group(CONHz). Further inves- 20 tigations have shown, that the said result isnot limited to the presence of the carbamyl group in the cyclicsulphamides. 0n the contra y, numerous experiments have shown theessential condition, that the process be started from compounds '4 whichcontain besides the sulphamyl group in the molecule a second 'or severalNH: groups in any manner of binding (combination whatever). Inconformity thereto the process according to the present inventionconsists in condensing sulph- 30 amides of cyclic organic compoundscontaining besides the sulphamyl group at least one substituted ornon-substituted NH: group, with aldehvdes and particularly withformaldehyde (CI-1:0). t

For the commercial manufacture or the new products by-products of thesaccharine manuiacture such as for instance parasulphamidobenzoic acid vC OOH lHl SOINH] Besides the In Austria July 20, 1929 (Cl. 26H)sulphamyl groups'also other NH: groups, especially also the carbamylgroup may be present.

' The reaction, when carried out by applying heat, leads finally toproducts which are insoluble and iniusible. Resins are obtainedas'intermediate products, which are soluble in organic solvents and givewater clear lacquers. By hardening the intermediate products in the heatand eventually under pressure, the glass-like hard final products areobtained therefrom. Also by condensation in the cold in the presence ofcatalysts, for instance of strong bases or acids intermediate productsare obtained, which can be brought into the final state by hardening.

The increase of the-NH: groups, which evidently renders possible thecourse of the reaction in the sense of the invention, can also beeffected by introducing one or several sulphamyl groups into aniline(CaHsNHz) phenylendiamine (CsH4(NH2)2) or into similar compounds, andcondensing the latter with formaldehyde.

The products obtained by the present process are, after the hardeninghas taken place, elastic, infusible and insoluble resins, which may beutilized as artificial masses for various purposes,

- e. g. as material for turnery ware.

The condensation'products may also be worked up into moldingcompositions with or without the addition of fillers, particularly offibrous materials.

The products obtained by are not only by their properties but also bytheir chemical composition distinguished from the resins obtained by theformaldehyde condensation of monosulphamides containing no further NH:groups, which are not capable of being hardened. As the primarymaterials contain more than one NH: group, each of these groups canreact with the Iormaldehyde so that the linking up can lead tomoleculeswhich are built up diflerently and greater than those obtainedfor instance by the condensation of p-toluolsulphamide the number andthe position (in the core 0, m, p

or in the side-chain) and also according to the the present process 7Besides aromatic compounds hydroaromatic or heterocyclic compounds mayalso he used, as primary material, provided that they answer the aboveindicated conditions. Carbazoltetrasulph-- 1 amide may be named as anexample. The compounds may also be polynuclear, in which case-condensedrings (for instance naphthalene) may be brought to condensation withaldehydes oralsoring systems linked directlyor bymeansofanygroupsandcontainin'gin total besides at least one sulphamyl groupat least one further NH: group in any binding whatever. Of thesepolynuclear compounds may be named for in stance pobsul sulfones', e. g.diphe- 85 nyl-sulfondisulphamide (CsHiSOsCsHflBOiNHs) a)polysulphamin'ated bensophenone and the like.

The condensation may be efiected eitherin the presence of solvents orwithout them, in the later case for instance by melting. Aqueousliquidsaswellasorganic ll uidsmaybeusedas solvents. Formaldehyde m beemployed in a solution or as gas or as polymeric formaldehyde or in theform of substances splitting off formaldehyde, ior instancehexamethylenetetramine ((CHshNs). Moreover in certain cases instead offormaldehyde other aldehydes may be used, for instance furfurol.Preferably equivalent or approximately equivalent amounts offormaldehyde areemployed, calculated on each NH: group present. Y I

The condensation may becarried out in the presence of catalysts. Acidsas well as bases act 65. as contacting agents. Moreover first of allinitial condensation products may be made, for instance methylolcompounds such as- Y so-Nncmon a s a\ communion or methylene derivativesof the amides such as-.

' /'BO|N=CH| c-n.

BO$N=CHI either in crystalline or amorphous form, and then convertedinto the resins by heating in solution or in absence of solvents bymelting. Purthermoretheprocessmay becarriedoutinsuch amannerthat thereactionisinthefirst stage conducted neutral or alkaline lay-means ofsubstances having a basic action (KOH, hexamethylenetetramine, saltshaving an alkaline reaction), in which case evidently first of allmethylol compounds are formed, and the condensation is then in a secondstage conducted acid, using acid, acid salts. esters, or else merelyconmztinuing the heating or by means of oxidizing agents. Theacidmaythcnbefullyorpartly neutraliaed.

During or after the condensation, formaldehyoe binding substances, suchas phenols, urea, 75 thiourea or amines may be added to the ,reactionmixture. Such compounds forming resins with formaldehyde may also iromthe very beginning be added andsubjected to the common condensation. Incertain cases mono-amides (for instance p-toluol-sulphamlde) may beincorporated with the mass during the operation. They also form resinswith formaldehyde, although these resins are not capable of beinghardened. If larger amounts of mono-amides are added, final products areobtained, which.

have a high melting point, but are not any more capable of beinghardened. These products are soluble in organic solvents.

The properties of the products thus obtained may furthermore be modifiedby incorporation ,of other, artificial or natural resins, celluloseesters, cellulose-ethers or other plastic In this manner products areobtained which can be worked up with oils or cellulose derivatives togive excellent lacquers. It should also he stated that while for thesake of uniformity of phraseology I have frequently used the term "urea"herein, I desire it to be understood, as clearly within the intendedscope of this disclosure. that such equivalent substitutes as thioureaor homologues of urea and thiourea may be employed in lieu thereof withpractically unchanged resuits.

Examples 1. p-sulphamidohenzamideformaldehyde to one molecule'of theamide) at boiling temperature in an apparatus with a refiux condenser.If boiling is not continued for a too long time the solution soongenerated re-' mains homogeneous and is after suitable thick-- ening -asfar as possible freed from water. Theresin still containing water iswhite in the cold and clear in the heat. It can be hardened by furtherheating and furnishes according to the degree of hardening a clear,supple and still soluble or a hard infusible and insoluble product.

The intermediate product obtained prior to the hardening is soluble inmany of the usual organic solvents such as alcohol, benzol, acetoneandthelikeandparticularlyalsoinmixturesof solvents. These solutions givetransparent and colorless lacquers.

If a small amount of acid is addedas condensing agent, the condensationproceeds considerably quicker and yields a hydrophobe resin, whichgelatinizes on further heating.

2. 350 grams of m-benzol-disulphamide SOsNHs SOaNHl are introduced mm240 cubic centimeters-of a 40% formaldehyde solution (to each SOsNH:

groupone CHaO group). The mixture is heamd up to boiling temperature. Ifthe dissolution has taken place, heating iscontinued for about 15minutes, whereafter the generated condensation product separates oncooling as a tough, brilliant white opaque resin. The product is 'washedand gives, when dissolved in a] l. a light lacquer. For obtaining aglass-like fin product it has to be hardened for longer time at 80' to100 C. The final product thus obtained is colorless, transparent,infusible and insoluble. Prior to the hardening, the resin may, byheating in a 5 vacuum. be partly freed from the water contained therein.

If the condensation is continued for a period longer than indicatedabove, an intermediate hour, whereafter the solution separates still inthe heat into an aqueous and an oily layer. The latter furnishes aftercooling a product similar 2 to that obtained by the mode according toExample 2.

4. 0.2 grams of R03 are dissolved in 100 ciibic centimeters of alcohol.Into this solution there are introduced 26 grams of paraformalde- 25hyde and 100 grams of m-benzol-disulphamide. The solution is heated andacidulated. After the condensation will be accomplished, about 20%acetone is added to the solution of resin thus obtained. A lacquer ofexcellent qualities is ch- 30 tained thereby.

' 5. 5 grams of xyloldisulphamide-- i)s u s-5007K:

somn,

45 of benzol disulphamide are introduced. After minutes a resin willseparate from the solution even in the cold state. The resin thusobtained is in this state still soluble in water and can be hardened bythe action of heat.

"I. If instead of the m-benzol-disulphamide amonochlorbenzoldisulphamide- Cl. CsHZ-SOaNHi) 55 SOsNHi oradichlorbenzoldisulphnmide- V somn. SO Hi r is used, solid condensationproducts are obtained,

capable of being hardened, but impaired transparency. Y

8. m-Toluoldisulphamideyields a resin similar to that from xyloldisulph-75 amide.

9. Aniline momma- NH: 0mg

(admin):

is brought to react with equivalent amounts of formaldehyde. The resinobtained thereby can be hardened, but gives brittle and clouded finalproducts.

.10. Similar products are obtained, if acetanilid- D-siflphamidh .mrcocmCoHi soiNHi is brought to react with one or two mols. of formaldehyde,or p-toluiline-disulphamidecm Gills-NH:

(soiNHowith two or three mols. of formaldehyde.

ll. m-Benzoldisulphamide is condensed with CHzO as set forth in Example2. A short time before the condensation is accomplished, further 20% ofbenzoldisulphamide are added and the condensation is continued. Theproduct obtained after hardening shows a-very high degree of hardness.

l2. '7 grams of benzoldisulphamide are dissolved in 4.42 cubiccentimeters of a 40% formaldehyde solution in the cold, adding also 22cubic centimeters of KOH. So much of 2NHC] is added, until theprecipitation setting in will be accomplished. Theprecipitate is first aresin-' like, then a cheese-like. product, which is washed with waterand then dried in vacuo. A white amorphous powder is obtained thereby,which readily furnishes a spirit lacquer. Moreover this powder can besubjected to hot pressing, either for itself alone or with fillingmaterials, (for instance cellulose).

'13. From phenol-disulphamidecmi ( INHa):

100 C., finely pulverized and the powder used for hot pressing. A hard,transparent product of horn like appearance is obtained.

15.- ni-Benzol-disulphamide is mixed with about 20% ofp-toluolmonosulphamide and to the mixture such an amount of formaldehydeis added. that one moi. of CHzO comes to each of the NH: groups presentin the mixture. After the condensation a product is obtained melting ata high melting point, which product is still soluble in organicsolvents.

16.'m-Benzol-d.isulphamide is heated with formaldehyde. After some time10 to 20% of thiourea are added to the solution. The resin whichseparates afterthe heating has been continued for short time, shows anincrease of. the hydrophobe properties incomparison with the resinproduced under the same conditions, but

without the addition of thiourea. v

, Two different products are obtained according to the amounts offormaldehyde used for the conden-ration. either .such as are equivalentto the bensol-dilulphamide or in equivalent relation toalltheNH:groupspresent.consequentlyalsoto 6 thoseofthethiourea.Inthelattercaseahomogeneous mixed condensation product is obtained.

What .I claim is:

1. A process for producing resin-like reaction 15 NH: group itself,.atleast one oi the sulphamyl or NH: groups being unsubstituted.

2. A process as defined in claim 1, wherein the condensation is carriedto such a stage that hardened products are formed.

8. A process as defined in claim 1, wherein the condensation is carriedout to an intermediate stage at which a condensation product capable ofbeing hardened is formed and converting such product into an infusiblefinal product by the action of heat and pressure.

4. A process as defined in claim 1, wherein the 'sulphamide compoundcontains besides the sulphamyl group at least one carbamyl (CONH:) D-

5.'A process as defined in claim 1, wherein the condensation is carriedout in the presence of an aldehyde binding substance selected from thefollowing group:phenols, urea, thiourea, amines and monamides.

there are at least two unsubstituted sulphamyl groups.

'7. A process as defined in claim 1, wherein the condensation is carriedout to an intermedicompound in an alkaline medium to produce a productwhich can be hardened and then continuing the condensation in an acidmedium.

10. A process for producing an infusible artificial resin whichcomprises dissolving without aspirin: heat in an alkaline aqueoussolution of formaldehyde, a sulphamide of a cyclic organic compoundcontaining besides an unsubstituted sulphamyl group at least one groupcontaining a substituted or unsubstituted NHs, adding an acid contentadequate to effect precipitation of a resinous body. separating thelatter from the liquid, washing it out and hardening by the-ap plicationof heat.

11. The process of producing a hardened resinlike condensation productwhich comprises reacting an aldehyde, an urea and a su phamidev of acyclic organic compound which contains besides the sulphamyl group. agroup containing a substituted or unsubstituted NH: radical. 12. Aprocess for producing resin-like reaction products which comprises thestep of condensing 6. A process as defined in claim 1, wherein ate stageat which a condensation product castituted or unsubstituted sulphamylgroup (SO:NH:) a substituted or unsubstituted NH: radical or the NH:group itself,'at leastone of the sulphamyl or NH: groups beingunsubstituted.

13. A process of producing resin-like reaction products which comprisesthe steps of condensing an aldehyde with a sulphamide of a cyclicorganic compound in an'alkaline medium to produce a product which can behardened.

14. A process for producing an infusible artificial resin whichcomprises dissolving without applying heat in .an alkaline aqueoussolution of formaldehyde, a sulphamide of a cyclic organic compoundcontaining besides one substituted or unsubstituted sulphamyl group(SO:NH:) a substituted or unsubstituted NH: radical or the NH: groupitself, at least one of the sulphamyl or NH: groups being unsubstituted.adding anacid content adequate to effect precipitation of a resinousbody. separating the latter from the liquid. washing it out, andhardening by the application of heat.

15. The process oi producing a hardened resinlike condensation productwhich comprises reacting an aldehyde, an urea and a sulphamide of acyclic organic compound which contains besides a substituted orunsubstituted sulphamyl group (SO:N'H:)' a substituted or unsubstitutedNH: radical or the NH: group itself, at least one of the sulphamyl orNH: groups being unsubstituted.

16. A process for producing an infusible artificial resin whichcomprises dissolving without applying heat in an alkaline aqueoussolution of formaldehyde, a sulphamide of a cyclic organic compoundcontaining besides at least one substituted or unsubstituted sulphamylgroup (SO:NH:)

,a group containing a substituted or unsubstituted NH: radical or asubstituted or unsubstituted NH: group itself, at least one of thesulphamyl or NH: groups being unsubstituted. adding an acid contentadequate to eifeot precipitation of a resinous body, separating thelatter from the liquid, washing it out, and hardening by the applicationof heat.

17. The process of producing a hardened resinllke condensation productwhich comprises reacting an aldehyde, an urea and a sulphamide of acyclic organic compound which contains besides at least one substitutedor unsubstituted sulphamyl group (SO:NH:) a group containing asubstituted or unsubstituted NH: radical, a substituted or unsubstitutedor NH: group itself. at least one of the sulphamyl or NH: groups beingunsubstituted. I

18. A hardened resin-like condensation product obtained by reacting analdehyde with a sulphamide of a cyclic organic compound containingbesides at least-one substituted or unsubamide compounds contain besidethe sulphamyl group, at least one carbanwl. (CONH:) group.

' 20. A resin-like product as defined in claim 23, wherein thecondensation is carried out in the presence of an aldehyde bindingsubstance selected from the following group :phenols, urea, thiourea,amines and monamides.

21. A resin-like product as defined in claim 23. wherein the reactingsulphamide contains at least two unsubstituted sulphamyl groups.

i an additional group containing a substituted or unsubstituted NH:radical. 24. The hardened resin-like condensation product resulting fromreacting an aldehyde an urea and a sulphamlde of a cyclic organiccompound which contains besides the sulphamyl group, a group containinga substituted or unsubstituted NH: radical.

. 25. A hardened resin-like condensation product obtained by reacting analdehyde with a sulphamide of a cyclic organic compound containingbesides a substituted or unsubstituted sulphamyl group (SO:NH:) asubstituted or unsubstituted NI-I: radical or the NH: group itself, atleast once! the sulphamyl or NH: groups being unsubstituted.

Patent No. 2 07 2, 971..

. numberedpatent re formula,for (8,0

'73, claims 19, 20, and 21 respectively,-

Certificate-of I ,GEOKG WALTER ,It is hereby certified that errorsappear -vin the rrection ss'ifollowsz Page 3, secon read (S0,NH age 1,second colu mn,. lines 65,. 68, and fort e claim reference numeral; 23"'read 18;

26. The hardened resin-like condensation product resulting from reactingan aldehyde, an urea and a sulphamide of a cyclic organic compound whichcontains besides a substituted or unsubstituted sulphamyi group (SO:NH:)a substituted or unsubstituted NH: radical or the NH: group itself, atleast one or the sulphamyl or NH: groups being unsubstituted.

27. The hardened resin-like condensation product resulting from reactingan aldehyde, an urea and a sulphamide of -a cyclic organic compoundwhich contains besides at least one substituted or unsubstitutedsulphamyl group (SO:NH:) a group containing a substituted orunsubstituted NH: radical or a substituted or unsubstituted NH: groupitself, at least one of the sulphan yl or NH: groups beingunsubstituted.

28. An intermediate condensation product capable of being hardenedresulting from the reaction of an aldehyde with a sulphamide of a cyclicorganic compound containing besides a substituted or unsubstitutedsulphamyl group (S0:NH:), a substituted or unsubstituted NH: radical orthe NH: group itself, at least one oi the sulphamyl or NH: groups beingunsubstituted.

' GEORG WALTER.

March 9, 1937.

andthat the said Letters Patent should be read with tha e b id thereinthat e Bi o may conform to the record of the case in the Patent 9mm. j

Signed and sealed thi's 27thday of April, A. D. 1937;

Acting 01PM.

i an additional group containing a substituted or unsubstituted NH:radical. 24. The hardened resin-like condensation product resulting fromreacting an aldehyde an urea and a sulphamlde of a cyclic organiccompound which contains besides the sulphamyl group, a group containinga substituted or unsubstituted NH: radical.

. 25. A hardened resin-like condensation product obtained by reacting analdehyde with a sulphamide of a cyclic organic compound containingbesides a substituted or unsubstituted sulphamyl group (SO:NH:) asubstituted or unsubstituted NI-I: radical or the NH: group itself, a'tleast once! the sulphamyl or NH: groups being unsubstituted.

Patent No. 2 07 2, 971..

. numberedpatent re formula,for (8,0

'73, claims 19, 20, and 21 respectively,-

Certificate-of ,GEOKG WALTER is 'hmby wtified h as a n -fi the 26. Thehardened resin-like condensation product resulting from reacting analdehyde, an urea and a sulphamide of a cyclic organic compound whichcontains besides a substituted or unsubstituted sulphamyi group (SO:NH:)a substituted or unsubstituted NH: radical or the NH: group itself, atleast one or the sulphamyl or NH: groups being unsubstituted.

27. The hardened resin-like condensation product resulting from reactingan aldehyde, an urea and a sulphamide of -a cyclic organic compoundwhich contains besides at least one substituted or unsubstitutedsulphamyl group (SO:NH:) a group containing a substituted orunsubstituted NH: radical or a substituted or unsubstituted NH: groupitself, at least one of the sulphan yl or NH: groups beingunsubstituted.

28. An intermediate condensation product capable of being hardenedresulting from the reaction of an aldehyde with a sulphamide of a cyclicorganic compound containing besides a substituted or unsubstitutedsulphamyl group (S0:NH:), a substituted or unsubstituted NH: radical orthe NH: group itself, at least one of the sulphamyl or NH: groups beingunsubstituted.

' GEORG WALTER.

March 9, 1937.

tion of the above rrection asifollows: Page 3, line 5, in the read(S0,NH age 1, second colu mn,. line's 65,. 68, and fort a claimreference numeral; 23 "'read 18;

andthat the said Letters Patent should be read with tha s b id thereinthat e Bi o may conform to the record of the case in the Patent 9mm. j

Signed and Saleem 27thday of April, A. D. 1937;

Acting 01PM.

